Method of producing ultraviolet luminescing silicates



March 14, 1961 A. H. HOEKSTRA METHOD OF PRODUCING ULTRAVIOLET LUMINESCING SILI'CATES Filed Sept. 18, 1956 INVENTOR AGE HlJlKE HOEKSTRA W A lies between 0.15 and 0.45,

Unite METHOD OF PRODUCING ULTRAVIOLET LUMINESCING SILICATES Age Hylke Hoekstra, Eindhoven, Netherlands, assignor,

by mesne assignments, to North American Philips Company, Inc., New York, N.Y., a corporation of Delaware Filed Sept. 18, 1956,'Ser. No. 610,607

' Claims priority, application Netherlands Oct. 3, 1955 7 Claims. (Cl. 252-3016) 'pr'oduced by such 'rnethods and to radiations sources comprising the combination of a gasand/ or vapour discharge tube and the said luminescent silicates.

It is well known that rays having a wavelength between 2900 A. and 3000 A. have a beneficial influence on human beings and animals. referred to as erythemal radiation. Consequently, radiation sources havebeen built which emit this radiation This radiation is frequently with suflicient intensity. A known radiation source of this kind comprises the combination of a gasand/or vapour discharge tube, more particularly a mercuryvapour discharge tube, and a screen coated with lumines- "cent materials which can be excited by the radiation- Y produced 'by the discharge to emiterythemal radiation.

The number of luminescent substances suiting this purpose is not very great, particularly if the requirement is to be satisfied that the conversion should be effected with satisfactory efficiency. 1

States PatentfQ" Cerium-activated compounds are known which can be excited by radiation of a wave-length of less than 2900 A. to emit erythemal radiation, however, they have a limitation in that, when they are used in a discharge tube, their conversion efficiency is satisfactory for a comparatively short period of time only. 1

One of the substances best suiting the above-mentioned purpose is a thallium-activated orthophosphate of calcium'and zinc.

stance for this purpose is a thallium-activated ortho--- phosphate of calcium and magnesium.

Another reasonably satisfactory sub- In a co-pending application SerialNo. 508,982, filed j May 17, 1955, now vUS. Patent 2,846,403, methods have been described of producing another substance which is i highly suited to the conversion of short-wave ultraviolet radiation into erythemal radiation.

lead-activated barium-zinc-silicate which is produced by heating a mixture of compounds .of barium, zinc, silicon Q and lead, which mixture on heating produces lead-ac- ,tivated barium-zinc silicate, in a non-reducing atmos phere to a temperature between 900 C. and 1100" C., for some hours. In producing this substance, as the initial material use is made of such amounts of the compounds that the proportion of the said elements in said mixture satisfy the following atomic ratio conditions Ba+Zn+Si j lies between 0.05 and 0.25,

2,975,143 Patented Mar. 14, 1961 lies between 0.40 and 0.80,

lies between 5 X10 and'10' ,since the discharge of such a tube emits a high amount of radiation of a wave-length of 2537 A. which is converted into the erythemal radiation with satisfactory efficiency.

As has also been described in this co-pending application of prior date, the luminescent substances thus produced offer the advantage over the known thalliumactivated luminescent substances emitting erythemal radiation that their production is simple since the activator is less volatile and less poisonous than the thallium.

In this co-pending application of prior date it is stated that a preferred ratio is obtained, if:

'Ba Ba+Zn+Si lies between 0.10 and 0.17,

Zn Ba-j-Zn-l-S lies between 0.30 and 0.45,

Ba+Zn+Si lies between 0.42 and 0.60,

. I APB Ba+Zn+Si lies between 5 10- and 10- I Continued tests of the luminescent products produced with the use of methods described in this co-pending ap plication of prior date have shown that these substances comprising a gasand/or vapour discharge tube and a layer of such a luminescent substance which is coated on the inner wall of the tube.

As is well known, in the manufacture of such a radiation source, the luminescent substance is usuallyapplied to the wall of the discharge vessel in that the substance This substance is a is suspended inaa liquid containing a binding agent,'after which the suspension is introduced into the discharge vessel, for example by raising it in the tube. Subsequent-- ly the suspension is drained off from the discharge vessel,

a layer consisting of the luminescent substance and the binding agent adhering to the wall. Subsequently .the discharge tube is dried and the binding agent, generally nitrocellulose, isevaporated and/or burnt by heating in a furnace. The luminescent substance adheres to the wall due to van der Waals forces.

In carrying out this normal method of coating, it was i found that the substances described in the above-mentioned application of prior date produced an unsatisfactory coating. When the binding agent was removed by burning, a comparatively large portion of the luminescent powder became detached. When the electrodes were subsequently mounted, in which process at least part of the tube is again heated to a high temperature, another part of the luminescent powder became detached. Consequently, in spite ofthe favourable -luminous properties of these luminescent substances, their use in manufacturing radiation sources presented great difliculty.

It is an object of the present invention to provide a I method of producing a luminescent substance" which exhibits the favourable luminous properties of the substances produced by the method described in the prior application, but does not become detached in the process of manufacturing a discharge tube in'which it is used.

According to the invention, in a method of producing a silicate which, when irradiated by the radiation produced in a gasand/or vapour discharge tube, emits shortwave ultra-violet radiation, a mixture of compounds of barium, zinc, magnesium, silicon and lead, which mixture on heating produces a lead-activated barium-magnesium-zinc silicate, and in which mixture the proportion of the said elements are such that they satisfy the following atomic ratio conditions:

lies between 0.05 and 0.25,

Zn-l-Mg lies between 0.15 and 0.45,

Z n Mg lies between 33 and 3, Si

Ba+Zn+Mg+Si lies between 0.40 and 0.80,

Pb Ba+Zn+Mg+Si lies between 5 x" and 10- is heated for a few hours in a non-reducing atmosphere to a temperature between 900 C. and 1100 C.

Substances produced by this method exhibit all the satisfactory luminous properties of the substances in accordance with the above-mentioned prior application, however, in addition it is found that they do not become detached from the wall of the discharge tube when they are introduced into this tube in a usual manner and the binding agent is removed by heating.

In order to provide a better understanding of this phenomenon, a differential thermal analysis was carried out of a number of compounds both with and without the inclusion of magnesium. The curves obtained proved that for preparations containing no magnesium there is a transition point at about 273 C.

When the magnesium content is gradually increased the molecular sum total of zinc and magnesium being kept constant, the transition point is shifted to higher temperatures and finally is no longer perceptible. Experiments in manufacturing discharge tubes have shown that the improvement of the adherence corresponds with the shifting and disappearance of the transition point.

The best products are obtained, if in the production in accordance with the invention, the atomic ratios are so chosen that:

Ba+Zn+Mg+Si lies between 0.15 and 0.20,

lies between 0.30 and 0.42,

lies between 33 and 3,

Si Ba+Zn+Mg+Si lies between 0.42 and 0.60,

lies between 5x10" and 10-.

In addition to the material improvement of the adherence, the substitution of magnesium for a part of the zinc provides some other advantages. When from 3 to 8 mol. percent of zinc are replaced by magnesium, the quantum efiiciency proves to increase by from 3 to 6%. When more than 8 mol. percent of zinc are replaced by magnesium, the quantum efliciency is slowly decreased and, when more than about 12 mol. percent of zinc are replaced, the quantum efiiciency even falls slightly below the quantum efiiciency of the compounds containing no magnesium. However, in this case there is a slight shift in the direction of shorter wave-lengths instead. The maximum emission, which initially was between 3000 A. and 3100 A. for the lower lead-contents and between 3000 A. and 3500 A. for the higher lead-contents, consequently shifts in the direction of the maximum of the erythemal sensitivity curve which, as is well known, lies at about 2970 A.

In a method in accordance with the invention, very suitable initial compounds comprise oxides, nitrates and carbonates of barium, zinc, magnesium or lead. The silicon is preferably added as an oxide. Mixtures of these compounds are also very suitable. The lead or the barium may also be added with advantage as fluorides, of which part also acts as a flux. Thus the production temperature is reduced and the crystallisation is promoted.

A few examples of production methods will now be described with reference to the drawing which shows some curves which, in units chosen at random, show the relationship between the wave-lengths of the emitted radiation and its intensity. All the curves have been taken with excitation by radiation having a wave-length of 2537 A.

Example I 12.35 gms. of BaCO 0.70 gms. of MgO 12.73 gms. of ZnO 15.8 gms. of SiO are mixed; the mixture is suspended in from ccs. to 250 ccs. of alcohol and ground in a ball-mill for 16 hours after the addition of 25 ccs. of an aqueous solution of Pb(NO in a concentration of 10- gram-molecule of Pb per cc. The suspension produced is dried by evaporation and the dry product is pulverized in a mortar, after which the powder is heated in a quartz crucible to a temperature of 700 C. in air in a furnace for 2 hours. After the crucible and its contents have been cooled in the furnace, the reaction product is again ground in a mortar. The powder produced is again heated in a furnace to a temperature of 1010 C. for 4 hours. This heat treatment is effected in a quartz crucible with closed cover. The crucible and its contents are subsequently cooled to room temperature. The product obtained is again ground and sieved. The spectral distribution is shown by curve 1 in the drawing. The quantum efficiency of the radiation emitted is substantially equal to that of a substance produced by a similar method but in which the MgO is replaced by an equivalent amount of 2110.

Example [I 35.14 gms. of BaCO 25.24 gms. of SiO 29.30 gms. of ZnO 0.35 gms. of BaF 1.61 gms. of MgO 1.12 gms. of PhD quantum efliciency also being substantially equal.

Example I II- 35.14 gms. of BaCO 25.24 grns. of SiO 26.04 gms. of ZnO 0.35 gms. of BaF 3.22 gms. of MgO 1.12 gms. of PbO Example IV 26.14 g. Ba(NO 36.00 g. sio 22.71 g. ZnO 0.70 g. PbF2 0.60 g. MgO

are mixed and ground in a mortar. The powder ob tained is heated in an alundum crucible in a furnace to 950 C. in air for 1 hour. The product is again ground in a mortar and heated in an alundum crucible in a furnace to 1050 C. in air for 1 hour. The crucible and its contents are cooled to room temperature in the furnace. The spectral distribution is substantially equal to that of a substance produced by the method described in Example I. The quantum efiiciency of the radiation is higher by about 6% than that of the corresponding substance in which the MgO is replaced by an equivalent amount of ZnO.

The luminescent substances produced by a method as described in any of the above examples can be applied in normal known manners as a luminescent layer to the inner wall of a glass envelope of a gasand/or vapourdischarge tube. As a binding agent use can be made of nitrocellulose, methyl-methacrylate, ammonium-alginate or similar substances, with the use of a suitable solvent, for example butyl-acetate.

What is claimed is:

1. An erythemal phosphor emitting ultraviolet radiation of a wave length of about 2900 A. to 3000 A. in response to ultraviolet radiation having a wave length of about 2537 A. and consisting essentially of a lead activated barium-magnesium-zinc silicate in which the elements satisfy the following atomic ratio conditions:

Ba 1W lies between 0.05 and 0.25,

Zn+Mg Ba-i-Zn-l-Mg-l-Si lies between 0.15 and 0.45

Zn fi lies between 33 and 3,

Si Ba+Zn+Mg+Si I lies between 0.40 and 0.80, and

Pb Ba+Zn+Mg+Si lies between 5 X" and 10- 2. An erythernal phosphor emitting ultraviolet radiation of a wave length of about 2900 A. to 3000 A. in response to ultraviolet radiation having a wave length of about 2537 A. and consisting essentially of a lead activated barium-magnesium-zinc silicate in which the elements satisfy the following atomic ratio conditions:

Ba Ba+Zn+Mg+ Si lies between 0.15 and 0.20,

6 Zn+Mg Ba+Zn+Mg+Si lies between 0.30 and 0.42, 5 s lies between 33 and 3,

Si Ba+Zn+Mg+Si lies between 0.42 and0.60, and.

Ba+Zn+Mg+Si lies between 5 X 10- and 10-.

3. The method of producing an erythemal phosphor emitting ultraviolet radiation in a wave length of about 2900 A. to 3000 A. in response to ultraviolet radiation having a wave length of about 2537 A. comprising the steps, forming -a mixture of barium, magnesium, zinc, silicon and lead compounds in proportions which upon heating forms a lead activated barium-magnesium zincs-ilicate in which the elements satisfy the following atomic ratio conditions:

Ba Ba+Zn+Mg+Si lies between about 0.05 and 0.25,

Zn+Mg Ba-i-Zn-i-Mg-f-Si lies between about 0.15 and 0.45,

lies between about 33 and 3,

Si Ba+Zn+Mg+Si lies between about 0.40 and 0.80, and

Pb Ba+Zn+Mg+Si lies between about 5 x10- and 10- and heating said mixture in a non-reducing atmosphere at a temperature between about 900 C. and 1100 C. for several hours.

4. The method of producing an erythemal phosphor emitting ultraviolet radiation in a wave length of about 2900 A. to 3000 A. in response to ultraviolet radiation having a wave length of about 2537 A. comprising the steps, forming a mixture of barium, magnesium, zine, silicon and lead compounds in proportions which upon heating forms a lead activated barium-magnesium zincsilicate in which the elements satisfy the following atomic ratio conditions:

lies between about 0.15 and 0.20,

Zn+Mg Ba+Zn+Mg+Si lies between about 0.30 and 0.42,

lies between about 33 and 3,

Si Ba+Zn+Mg+Si lies between about 0.42 and 0.60, and

7 Pb Ba-i-Zh-i-Mg-f-Si lies between about 5 10- and 10- and heating said mixture inia non-reducing atmosphere at a temperature between about 900 and 1100 C. for several hours. l V v 5. The method of claim ,4 in which at least one of the compounds used is an oxide.

6. The method of claim 4 in which the barium compound is a barium fluoride. i

7. The method of claim 4 m which the lead compound is a lead fluoride.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Butler: J. Electrochem. SOC. March 1950, V01. 97, N0.

3, pages 83-91. 

1. AN ERYTHEMAL PHOSPHOR EMITTING ULTRAVIOLET RADIATION OF WAVE LENGTH OF ABOUT 2900 A. TO 3000 A. IN RESPONSE TO ULTRAVIOLET RADIATION HAVING A WAVE LENGTH OF ABOUT 2537 A. AND CONSISTING ESSENTIALLY OF A LEAD ACTIVATED BARIUM-MAGNESIUM-ZINC SILICATE IN WHICH THE ELEMENTS SATISFY THE FOLLOWING ATOMIC RATIO CONDITIONS:
 3. THE METHOD OF PRODUCING AN ERYTHEMAL PHOSPHOR EMITTING ULTRAVIOLET RADIATION IN A WAVE LENGTH OF ABOUT 2900 A. TO 3000 A. IN RESPONSE TO ULTRAVIOLET RADIATION HAVING A WAVE LENGTH OF ABOUT 2537 A. COMPRISING THE STEPS, FORMING A MIXTURE OF BARIUM, MAGNESIUM, ZINC, SILICON AND LEAD COMPOUNDS IN PROPORTIONS WHICH UPON HEATING FORMS A LEAD ACTIVATED BARIUM-MAGNESIUM ZINCSILICATE IN WHICH THE ELEMENT SATISFY THE FOLLOWING ATOMIC RATIO CONDITIONS: 